Semiconductor device and manufacturing method thereof

ABSTRACT

In a method of manufacturing a negative capacitance structure, a dielectric layer is formed over a substrate. A first metallic layer is formed over the dielectric layer. After the first metallic layer is formed, an annealing operation is performed, followed by a cooling operation. A second metallic layer is formed. After the cooling operation, the dielectric layer becomes a ferroelectric dielectric layer including an orthorhombic crystal phase.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of application Ser. No.15/798,273 filed on Oct. 30, 2017, the entire disclosures of which areincorporated herein by reference.

TECHNICAL FIELD

The disclosure relates to semiconductor integrated circuits, and moreparticularly to semiconductor devices including negative capacitancefield effect transistors (NC FETs).

BACKGROUND

The subthreshold swing is a feature of a transistor's current-voltagecharacteristic. In the subthreshold region the drain current behavior issimilar to the exponentially increasing current of a forward biaseddiode. A plot of logarithmic drain current versus gate voltage withdrain, source, and bulk voltages fixed will exhibit approximatelylogarithmic linear behavior in this metal-oxide-semiconductor (MOS) FEToperating region. To improve the subthreshold properties, a negativecapacitance field effect transistor (NC FET) using a ferroelectricmaterial has been proposed.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the standard practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIGS. 1A and 1B shows cross sectional views ofmetal-insulator-semiconductor (MIS) FET-type NC FETs, and FIG. 1C showsa cross sectional view of ametal-insulator-metal-insulator-semiconductor (MIMIS) FET-type NC FET.

FIGS. 2A, 2B, 2C and 2D show various stages of manufacturing operationsfor a negative capacitance structure in accordance with an embodiment ofthe present disclosure.

FIGS. 3A, 3B, 3C and 3D show various atomic structures of HfO₂.

FIG. 4 shows X-Ray Diffraction (XRD) measurement results.

FIGS. 5 and 6 show electron energy loss spectroscopy (EELS) measurementresults.

FIGS. 7A, 7B, 7C and 7D show various stages of manufacturing operationsfor an NC FET in accordance with an embodiment of the presentdisclosure.

FIGS. 8A, 8B, 8C and 8D show various stages of manufacturing operationsfor an NC FET in accordance with an embodiment of the presentdisclosure.

FIGS. 9A, 9B and 9C show various stages of manufacturing operations foran NC FET in accordance with an embodiment of the present disclosure.

FIGS. 10A, 10B and 10C show various stages of manufacturing operationsfor an NC FET in accordance with an embodiment of the presentdisclosure.

FIGS. 11A, 11B and 11C show various stages of manufacturing operationsfor an NC FET in accordance with an embodiment of the presentdisclosure.

FIGS. 12A, 12B and 12C show various stages of manufacturing operationsfor an NC FET in accordance with an embodiment of the presentdisclosure.

FIGS. 13A, 13B and 13C show various stages of manufacturing operationsfor an NC FET in accordance with an embodiment of the presentdisclosure.

FIGS. 14A, 14B, 14C and 14D show manufacturing operations for an NC FETin accordance with another embodiment of the present disclosure.

FIGS. 15A, 15B, 15C and 15D show manufacturing operations for an NC FETin accordance with an embodiment of the present disclosure.

DETAILED DESCRIPTION

It is to be understood that the following disclosure provides manydifferent embodiments, or examples, for implementing different featuresof the invention. Specific embodiments or examples of components andarrangements are described below to simplify the present disclosure.These are, of course, merely examples and are not intended to belimiting. For example, dimensions of elements are not limited to thedisclosed range or values, but may depend upon process conditions and/ordesired properties of the device. Moreover, the formation of a firstfeature over or on a second feature in the description that follows mayinclude embodiments in which the first and second features are formed indirect contact, and may also include embodiments in which additionalfeatures may be formed interposing the first and second features, suchthat the first and second features may not be in direct contact. Variousfeatures may be arbitrarily drawn in different scales for simplicity andclarity. In the accompanying drawings, some layers/features may beomitted for simplification.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The device may be otherwise oriented (rotated 90 degrees orat other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly. In addition, the term“made of” may mean either “comprising” or “consisting of.” Further, inthe following fabrication process, there may be one or more additionaloperations in/between the described operations, and the order ofoperations may be changed.

To lower subthreshold swing (S.S.) of a field effect transistor (FET), anegative-capacitance (NC) technology, such as integrating ferroelectric(FE) materials, provides a feasible solution to lower V_(DD) (powersupply) significantly, and achieves an FET having a steep S.S. for lowpower operation.

In an NC FET, a capacitor (e.g., a ferroelectric (FE) capacitor) havinga negative capacitance is connected to a gate of a MOS FET in series.The ferroelectric negative capacitor can be a separate capacitorconnected by a conductive layer (e.g., wire/contact) to the gate of theMOS FET, in some embodiments. In other embodiments, one of theelectrodes of the negative capacitor is a gate electrode of the MOS FET.In such a case, the negative capacitor is formed within sidewall spacersof the MOS FET.

In conventional devices, high-K gate materials, such as HfO₂, areusually an amorphous layer. However, the un-doped HfO₂ is amorphous andparaelectric, which does not show a negative-capacitance effect.Ferroelectric materials having Perovskite structure, such as PZT orBaTiO₃, have excellent FE characteristics. However, these materialsstill pose difficulties because formation of these materials is notfully compatible with silicon-based semiconductors, and theferroelectric properties degrade with reducing the thickness thereof dueto a size effect.

In the present disclosure, a doped HfO₂ layer having an orthorhombiccrystal phase, which shows a ferroelectric property, and its productionmethods are provided.

FIGS. 1A and 1B show cross sectional views ofmetal-insulator-semiconductor (MIS) FET-type NC FETs, and FIG. 1B showsa cross sectional view of ametal-insulator-metal-insulator-semiconductor (MIMIS) FET-type NC FET.Although FIGS. 1A-1C show NC FETs of a planar MOS transistor structure,fin FETs and/or gate-all-around FETs can be employed.

As shown in FIG. 1A, an MIS NC FET includes a substrate 100, a channel101 and source and drain 102. The source and drain 102 are appropriatelydoped with impurities. Further, the source and drain and the channel(active regions) are surrounded by an isolation insulating layer (notshown), such as shallow trench isolation (STI), made of, for example,silicon oxide.

An interfacial layer 103 is formed over the channel layer 101, in someembodiments. The interfacial layer 103 is made of silicon oxide havingthickness in a range from about 0.5 nm to about 1.5 nm in someembodiments.

A ferroelectric dielectric layer 105 is disposed over the interfaciallayer 103. The ferroelectric dielectric layer 105 includes HfO₂ dopedwith one or more elements selected from the group consisting of Si, Zr,Al, La, Y, Gd and Sr. In some embodiments, the ferroelectric dielectriclayer 105 includes HfO₂ doped with Si and/or Zr. In certain embodiments,the ferroelectric dielectric 105 layer includes HfO₂ doped with Si in anamount of 2-6 mol % or HfZrO₂ (Hf:Zr=1:1). In the present disclosure,the ferroelectric dielectric layer 105 includes an orthorhombic crystalphase. The orthorhombic crystal of the ferroelectric dielectric layer105 is polycrystalline in some embodiments. The thickness of theferroelectric dielectric layer 105 is in a range from about 1.0 nm toabout 5 nm in some embodiments, and may be formed by a suitable processsuch as ALD or CVD.

A gate electrode layer 106 is disposed over the ferroelectric dielectriclayer 105. The gate electrode layer 106 includes one or more metalliclayers. In some embodiments, the gate electrode layer 106 includes afirst conductive layer (a capping layer) disposed on the ferroelectricdielectric layer 105, a second layer (a barrier layer) disposed on thefirst conductive layer, a third conductive layer (a work functionadjustment layer) disposed on the second conductive layer, a fourthconductive layer (a glue layer) disposed on the third conductive layerand/or a fifth conductive layer (a main gate metal layer) disposed onthe fourth conductive layer.

The capping layer includes a TiN based material, such as TiN and TiNdoped with one or more additional elements. In some embodiments, the TiNlayer is doped with Si. The barrier layer includes TaN in someembodiments.

The work function adjustment layer includes one or more layers ofconductive material, such as a single layer of TiN, TaN, TaAlC, TiC,TaC, Co, Al, TiAl, HfTi, TiSi, TaSi or TiAlC, or a multilayer of two ormore of these materials. For the n-channel FinFET, one or more of TaN,TaAlC, TiN, TiC, Co, TiAl, HfTi, TiSi and TaSi is used as the workfunction adjustment layer, and for the p-channel FinFET, one or more ofTiAlC, Al, TiAl, TaN, TaAlC, TiN, TiC and Co is used as the workfunction adjustment layer.

The glue layer includes Ti, TiN and/or TaN in some embodiments. The maingate metal layer includes a metal selected from a group of W, Cu, Ti, Aland Co.

Further, sidewall spacers 109 are formed on opposing side faces of thegate structure as shown in FIG. 1A. The sidewall spacers 109 include oneor more layers of insulating material, such as silicon oxide, siliconnitride and silicon oxynitride.

FIG. 1B shows a cross sectional views of a metal-insulator-semiconductor(MIS) FET-type NC FET in accordance with another embodiment. In FIG. 1B,the interfacial layer 103 is has a flat shape, and the ferroelectricdielectric layer 105 is conformally formed in the gate space and has aheight substantially equal to the height of the gate electrode layer106.

In FIG. 1C, similar to FIGS. 1A and/or 1B, a channel 101 and source anddrain 102 are formed on a substrate 100. A first gate dielectric layer113 is disposed over the channel 101. The first gate dielectric layer113 includes one or more high-k dielectric layers (e.g., having adielectric constant greater than 3.9) in some embodiments. For example,the one or more gate dielectric layers may include one or more layers ofa metal oxide or a silicate of Hf, Al, Zr, combinations thereof, andmulti-layers thereof. Other suitable materials include La, Mg, Ba, Ti,Pb, Zr, in the form of metal oxides, metal alloy oxides, andcombinations thereof. Exemplary materials include MgO_(x), SiN(Si₃N₄),Al₂O₃, La₂O₃, Ta₂O₃, Y₂O₃, HfO₂, ZrO₂, GeO₂, Hf_(x)Zr_(1-x)O₂, Ga₂O₃,Gd₂O₃, TaSiO₂, TiO₂, HfSiON, YGe_(x)O_(y), YSi_(x)O_(y) and LaAlO₃, andthe like. In certain embodiments, HfO₂, ZrO₂ and/or Hf_(x)Zr_(1-x)O₂ isused. The formation methods of first gate dielectric layer 113 includemolecular-beam deposition (MBD), atomic layer deposition (ALD), physicalvapor deposition (PVD), chemical vapor deposition (CVD), and the like.In some embodiments, the first gate dielectric layer 113 has a thicknessof about 1.0 nm to about 5.0 nm.

In some embodiments, an interfacial layer (not shown) may be formed overthe channel 101 prior to forming the first gate dielectric layer 113,and the first gate dielectric layer 113 is formed over the interfaciallayer.

A first gate electrode 114 as an internal electrode is disposed on thefirst gate dielectric layer 113. The first gate electrode 114 may be oneor more metals, such as W, Cu, Ti, Ag, Al, TiAl, TiAlN, TaC, TaCN,TaSiN, Mn, Co, Pd, Ni, Re, Ir, Ru, Pt, and Zr. In some embodiments, thefirst gate electrode 114 includes one or more of TiN, WN, TaN, and Ru.Metal alloys such as Ti—Al, Ru—Ta, Ru—Zr, Pt—Ti, Co—Ni and Ni—Ta may beused and/or metal nitrides, such as WN_(x), TiN_(x), MoN_(x), TaN_(x),and TaSi_(x)N_(y) may also be used. In some embodiments, at least one ofW, Ti, Ta, TaN and TiN is used as the first gate electrode 114. In someembodiments, the first gate electrode 114 includes a work functionadjustment layer.

A ferroelectric dielectric layer 115 is formed on the first gateelectrode 114. The ferroelectric dielectric layer 115 includes HfO₂doped with one or more elements selected from the group consisting ofSi, Zr, Al, La, Y, Gd and Sr. In some embodiments, the ferroelectricdielectric layer 115 includes HfO₂ doped with Si and/or Zr. In certainembodiments, the ferroelectric dielectric 115 layer includes HfO₂ dopedwith Si in an amount of 2-6 mol % or HfZrO₂ (Hf:Zr=1:1). In the presentdisclosure, the ferroelectric dielectric layer 115 includes anorthorhombic crystal phase. The orthorhombic crystal of theferroelectric dielectric layer 115 is polycrystalline in someembodiments. The thickness of the ferroelectric dielectric layer 115 isin a range from about 1.0 nm to about 5 nm in some embodiments, and maybe formed by a suitable process such as ALD or CVD.

Further, a second gate electrode 116 as an external gate is disposed onthe ferroelectric dielectric layer 115. The second gate electrode 116may be a metal selected from a group of W, Cu, Ti, Ag, Al, TiAl, TiAlN,TaC, TaCN, TaSiN, Mn, Co, Pd, Ni, Re, Ir, Ru, Pt, and Zr. The secondgate electrode 116 is made of the same material as or different materialfrom the first gate electrode 114. Further, sidewall spacers 119 areformed on opposing side faces of the gate structure as shown in FIG. 1C.The sidewall spacers 119 include one or more layers of insulatingmaterial, such as silicon oxide, silicon nitride and silicon oxynitride.

As shown in FIGS. 1A-1C, the ferroelectric dielectric layers 105 and 115and the first gate dielectric layer 113 have a “U-shape” in the crosssection, having a thin center portion and thick side portions in thevertical direction.

FIGS. 2A, 2B, 2C and 2D show various stages of manufacturing operationsfor a negative capacitance structure in accordance with an embodiment ofthe present disclosure. It is understood that additional operations canbe provided before, during, and after the processes shown by FIGS.2A-2D, and some of the operations described below can be replaced oreliminated, for additional embodiments of the method. The order of theoperations/processes may be interchangeable. Material, configuration,dimensions and/or processes the same as or similar to the foregoingembodiments described with FIGS. 1A-1C may be employed in the followingembodiments, and detailed explanation thereof may be omitted.

As shown in FIG. 2A, an interfacial layer 20 is formed on a substrate10. In some embodiments, the substrate 10 is made of a suitableelemental semiconductor, such as silicon, diamond or germanium; asuitable alloy or compound semiconductor, such as Group-IV compoundsemiconductors (silicon germanium (SiGe), silicon carbide (SiC), silicongermanium carbide (SiGeC), GeSn, SiSn, SiGeSn), Group III-V compoundsemiconductors (e.g., gallium arsenide (GaAs), indium gallium arsenide(InGaAs), indium arsenide (InAs), indium phosphide (InP), indiumantimonide (InSb), gallium arsenic phosphide (GaAsP), or gallium indiumphosphide (GaInP)), or the like. Further, the substrate 10 may includean epitaxial layer (epi-layer), which may be strained for performanceenhancement, and/or may include a silicon-on-insulator (SOI) structure.

In some embodiments, the interfacial layer 20 is a silicon oxide, whichmay be formed by chemical reactions. For example, a chemical siliconoxide may be formed using deionized water+ozone (DIO₃), NH₄OH+H₂O₂+H₂O(APM), or other methods. Other embodiments may utilize a differentmaterial or processes for the interfacial layer. In some embodiments,the interfacial layer 20 has a thickness of about 0.5 nm to about 1.5nm.

Then, a dielectric layer 30 is formed over the interfacial layer 20. Thedielectric layer 30 includes HfO₂ doped with one or more elementsselected from the group consisting of Si, Zr, Al, La, Y, Gd and Sr.

The formation methods of the dielectric layer 30 include molecular-beamdeposition (MBD), atomic layer deposition (ALD), physical vapordeposition (PVD), chemical vapor deposition (CVD), and the like. In someembodiments, HfO₂ doped with Zr can be formed by ALD using HfCl₄ and H₂Oas a first precursor and ZrCl₄ and H₂O as a second precursor at atemperature in a range from about 200° C. to 400° C. In a case of HfO₂doped with Si, SiH₄, Si₂H₆, and/or SiH₂Cl₂ or other suitable siliconsource gas may be used. The dielectric layer 30 as deposited isamorphous and paraelectric. The thickness of the dielectric layer 30 isin a range from about 1 nm to about 5 nm in some embodiments.

After the dielectric layer 30 is formed, a capping layer 40 is formed onthe dielectric layer 30, as shown in FIG. 2B. The capping layer 40includes a TiN based material, such as TiN and TiN doped with one ormore additional elements, in some embodiments. In some embodiments, theTiN layer is doped with Si. The capping layer 40 can be formed by ALD,CVD or physical vapor deposition including sputtering or any othersuitable methods. When ALD is utilized, the ALD is performed at atemperature in a range from about 400° C. to about 500° C. in someembodiments. The thickness of the capping layer 40 is in a range fromabout 1 nm to about 5 nm in some embodiments.

After the capping layer 40 is formed, an annealing operation isperformed as shown in FIG. 2C. The annealing operation is performed at atemperature in a range from about 700° C. to about 1000° C. in an inertgas ambient, such as N₂, Ar and/or He. The annealing period is in arange from about 10 sec to 1 min in some embodiments. After theannealing, a cooling operation is performed. In some embodiments, thesubstrate is cooled down to less than 100° C. or to room temperature(about 25° C.). The annealing operation after the capping layer 40 isformed provides a driving force for the doped HfO₂ structure transitionfrom amorphous phase to high-temperature tetragonal phase, and cappinglayer 40 provides the mechanical stress needed for the crystallinetransition from the high-temperature tetragonal phase to thehigh-pressure ferroelectric orthorhombic phase during cooling.

In some embodiments, after the capping layer 40 is formed, an amorphoussilicon layer is formed on the capping layer 40, and then the annealingoperation is performed. After the annealing operation and coolingoperation are performed, the amorphous silicon layer is removed.

After the cooling operation, a barrier layer 52 made of, for example,TaN, is formed over the capping layer 40, as shown in FIG. 2D. Thebarrier layer 52 can be formed by ALD, CVD or physical vapor depositionincluding sputtering or any other suitable methods. When ALD isutilized, the ALD is performed at a temperature in a range from about300° C. to about 400° C. in some embodiments. The thickness of thebarrier layer 52 is in a range from about 1 nm to about 5 nm in someembodiments. In some embodiments, the annealing operation to convert theamorphous structure to the orthorhombic structure may be performed afterthe barrier layer 52 is formed.

Further, a work function adjustment layer 54 is formed on the barrierlayer 52. In some embodiments, the work function adjustment layer 54includes TiN for a p-type transistor and TiAl for an n-type transistor.Any other suitable metallic material can be used as the work functionadjustment layer 54. In some embodiments, a TiAl layer is also formed ona TiN work function adjustment layer for a p-type transistor. The workfunction adjustment layer 54 can be formed by ALD, CVD or physical vapordeposition including sputtering or any other suitable methods. When ALDis utilized, the ALD is performed at a temperature in a range from about300° C. to about 400° C. in some embodiments. The thickness of the workfunction adjustment layer 54 is in a range from about 1 nm to about 5 nmin some embodiments.

Further, a main gate metal layer 58 is formed over the work functionadjustment layer 54. The main gate metal layer 58 includes one or moremetals, such as W, Cu, Ti, Al and Co, or other suitable material. Insome embodiments, when the main gate metal layer 58 is W, a glue layer56 is formed on the work function adjustment layer 54. In someembodiments, the glue layer 56 is Ti. As shown in FIG. 2D, the gateelectrode 50 may include a barrier layer 52 disposed on the cappinglayer 40, a work function adjustment layer 54 disposed on the barrierlayer 52, a glue layer 56 disposed on the work function adjustment layer54 and a main gate metal layer 58. In some embodiments, the cappinglayer may be considered as a part of the gate electrode 50.

FIGS. 3A, 3B, 3C and 3D show various atomic structures of HfO₂. FIG. 3Ashows the amorphous structure of the doped HfO₂ as deposited. Byapplying heat, the amorphous structure transitions to a tetragonalcrystal structure (phase), as shown in FIG. 3B. When the heated HfO₂having a tetragonal crystal structure is cooled with a capping metalthereon, the HfO₂ becomes an orthorhombic crystal structure (phase), asshown in FIG. 3C. If the heated HfO₂ having a tetragonal crystalstructure is cooled without the capping metal thereon, the HfO₂ becomesa mixture of a monolithic crystal structure (left) and a tetragonalcrystal structure (right), as shown in FIG. 3D. The orthorhombic HfO₂has a non-centrosymmetric structure, and thus spontaneous polarizationis generated by four oxygen ions displacement. Accordingly, betterferroelectric properties can be obtained by the orthorhombic HfO₂.

FIG. 4 shows X-Ray Diffraction (XRD) measurement results. The samplesare a 3-nm thick doped HfO₂ as deposited and a 3-nm thick doped HfO₂after the annealing operation with a capping layer. The doped HfO₂ asdeposited shows a broad spectrum indicating amorphous structure. Incontrast, the doped HfO₂ after the annealing operation with a cappinglayer shows peaks corresponding to orthorhombic phase.

FIGS. 5 and 6 show electron energy loss spectroscopy (EELS) measurementresults. As set forth above, after the dielectric layer 30 is convertedto an orthorhombic phase, additional layers are formed with some thermaloperations. The dopant elements in HfO₂ such as semiconductor material(Si) and metal elements (Zr, Al, La, Y, Gd and/or Sr) introduced byin-situ doping during the ALD growth are substantially uniformlydistributed in the doped HfO₂ layer. As shown in FIGS. 5 and 6, Tiarising from the capping layer 40 (TiN based material) diffuses into theHfZrO₂ layer. When a TiAl layer is used as a work function adjustmentlayer 54 for an n-type transistor, Al may also diffuse into the HfZrO₂layer, as shown in FIG. 5. In some embodiments, the HfZrO₂ layerincludes Al in an amount of 5-7 mol %. When a TiN layer is used as awork function adjustment layer 54 for a p-type transistor, Tioriginating from the TiN work function adjustment layer may also diffuseinto the HfZrO₂ layer, as shown in FIG. 6. For the p-type transistor, Almay not diffuse into the HfZrO₂ layer (below a detection limit), even ifa TiAl layer is formed on the TiN work function adjustment layer. Insome embodiments, the HfZrO₂ layer includes Ti in an amount of 2-5 mol%.

In some embodiments, the ferroelectric HfO₂ layer consists of anorthorhombic crystal phase. In other embodiments, the ferroelectric HfO₂layer is substantially formed by an orthorhombic crystal phase. In sucha case, the orthorhombic crystal phase is about 80% or more of theferroelectric HfO₂ layer, and the remaining phases may be amorphous, amonolithic phase and/or a tetragonal phase.

FIGS. 7A-13C show various stages of manufacturing operations for an NCFET in accordance with an embodiment of the present disclosure. It isunderstood that additional operations can be provided before, during,and after the processes shown by FIGS. 7A-13C, and some of theoperations described below are replaced or eliminated, for additionalembodiments of the method. The order of the operations/processes may beinterchangeable. Material, configuration, dimensions and/or processesthe same as or similar to the foregoing embodiments described with FIGS.1A-2D may be employed in the following embodiments, and detailedexplanation thereof may be omitted.

FIG. 7A shows a perspective view and FIG. 7B is a cross sectional viewalong the X direction, showing one of various stages of themanufacturing operation according to an embodiment of the presentdisclosure. As shown in FIGS. 7A and 7B, a substrate 200 is provided. Insome embodiments, the substrate 200 is made of a suitable elementalsemiconductor, such as silicon, diamond or germanium; a suitable alloyor compound semiconductor, such as Group-IV compound semiconductors(silicon germanium (SiGe), silicon carbide (SiC), silicon germaniumcarbide (SiGeC), GeSn, SiSn, SiGeSn), Group III-V compoundsemiconductors (e.g., gallium arsenide (GaAs), indium gallium arsenide(InGaAs), indium arsenide (InAs), indium phosphide (InP), indiumantimonide (InSb), gallium arsenic phosphide (GaAsP), or gallium indiumphosphide (GaInP)), or the like. Further, the substrate 200 may includean epitaxial layer (epi-layer), which may be strained for performanceenhancement, and/or may include a silicon-on-insulator (SOI) structure.The upper portion of the substrate 200 can be multilayers of Si andSiGe.

FIG. 7C shows a perspective view and FIG. 7D is a cross sectional viewalong the X direction, showing one of various stages of themanufacturing operation according to an embodiment of the presentdisclosure. As shown in FIGS. 7C and 7D, fin structures 210 are formedby etching the substrate 200 and forming an isolation insulating layer220. The fin structures 210 may be patterned by any suitable method. Forexample, the fin structures 210 may be patterned using one or morephotolithography processes, including double-patterning ormulti-patterning processes. Generally, double-patterning ormulti-patterning processes combine photolithography and self-alignedprocesses, allowing patterns to be created that have, for example,pitches smaller than what is otherwise obtainable using a single, directphotolithography process. For example, in one embodiment, a sacrificiallayer is formed over a substrate and patterned using a photolithographyprocess. Spacers are formed alongside the patterned sacrificial layerusing a self-aligned process. The sacrificial layer is then removed, andthe remaining spacers, or mandrels, may then be used to pattern the finstructures 210. In some embodiments, the width of the fin structures 210is in a range from about 4 nm to about 10 nm and the pitch of the finstructures 210 is in a range from about 10 nm to about 50 nm.

Then, an insulating material layer 220 is formed over the finstructures, thereby embedding the fin structures. The insulatingmaterial layer 220 may be made of suitable dielectric materials such assilicon oxide, silicon nitride, silicon oxynitride, fluorine-dopedsilicate glass (FSG), low-k dielectrics such as carbon doped oxides,extremely low-k dielectrics such as porous carbon doped silicon dioxide,a polymer such as polyimide, combinations of these, or the like. In someembodiments, the insulating material layer 220 is formed through aprocess such as CVD, flowable CVD (FCVD), or a spin-on-glass process,although any acceptable process may be utilized. Subsequently, portionsof the insulating material layer 220 extending over the top surfaces ofthe fin structures 210 are removed using, for example, an etch process,chemical mechanical polishing (CMP), or the like, as shown in FIGS. 7Cand 7D.

FIG. 8A shows a perspective view and FIG. 8B is a cross sectional viewalong the X direction, showing one of various stages of themanufacturing operation according to an embodiment of the presentdisclosure. Further, as shown in FIGS. 8A and 8B, the insulatingmaterial layer 220 is recessed so that the upper portions of the finstructures 210 are exposed. The recessed insulating material layer 220is called an isolation insulating layer or a shallow trench isolation(STI). The height of the exposed fin structures 210 measured from theupper surface of the isolation insulating layer 220 is in a range about30 nm to about 100 nm in some embodiments.

FIG. 8C shows a perspective view and FIG. 8D is a cross sectional viewalong the X direction, showing one of various stages of themanufacturing operation according to an embodiment of the presentdisclosure. Subsequently, a dummy gate dielectric layer 215 is formedover the upper portions of the fin structure 210, as shown in FIGS. 8Cand 8D. The dummy gate dielectric layer 215 is a silicon oxide layerformed by CVD or ALD, in some embodiments. The thickness of the dummygate dielectric layer 215 is in a range from about 1 nm to about 3 nm insome embodiments.

Then, a polysilicon layer 230 is formed over the dummy gate electrodelayer 215, and further a hard mask layer is formed on the polysiliconlayer. The hard mask layer is patterned into hard mask pattern 235 bysuitable lithography and etching operations, as shown in FIGS. 9A-9C.The hard mask pattern 235 includes one or more layers of insulatingmaterial, such as silicon oxide and silicon nitride, in someembodiments.

FIG. 9A shows a perspective view, FIG. 9B is a cross sectional viewalong the Y direction and FIG. 9C is a cross sectional view along the Xdirection, showing one of various stages of the manufacturing operationaccording to an embodiment of the present disclosure. By using the hardmask pattern 235 as an etching mask, the polysilicon layer is patternedinto dummy gate electrodes 230, as shown in FIGS. 9A-9C. In someembodiments, the width of the dummy gate electrode 230 is in a rangefrom about 8 nm to about 20 nm.

FIG. 10A shows a perspective view, FIG. 10B is a cross sectional viewalong the Y direction and FIG. 10C is a cross sectional view along the Xdirection, showing one of various stages of the manufacturing operationaccording to an embodiment of the present disclosure. Sidewall spacers240 are formed on opposing side faces of the dummy gate electrodes 230.The sidewall spacers 240 include one or more layers of insulatingmaterial, such as silicon oxide, silicon nitride and silicon oxynitride.Moreover, source/drain epitaxial layers 250 are formed over source/drainregions of the fin structures 210. The source/drain epitaxial layer 250includes SiP, SiAs, SiGeP, SiGeAs, GeP, GeAs, and/or SiGeSn or othersuitable material for an n-type FET, and SiB, SiGa, SiGeB, SiGeGa, GeB,GeGa and/or SiGeSn or other suitable material for a p-type FET. Thethickness of the source/drain epitaxial layers 250 is in a range fromabout 3 nm to about 8 nm in some embodiments. In some embodiments, analloy layer, such as, a silicide layer, is formed over the source/drainepitaxial layers 250.

FIG. 11A shows a perspective view, FIG. 11B is a cross sectional viewalong the Y direction and FIG. 11C is a cross sectional view along the Xdirection, showing one of various stages of the manufacturing operationaccording to an embodiment of the present disclosure. Subsequently, acontact etch stop layer (CESL) 245 and an interlayer dielectric layer260 are formed, and a planarization operation, such as a CMP operation,is performed to exposed upper surfaces of the dummy gate electrodes 230,as shown in FIGS. 11A-11C.

In some embodiments, the CESL layer 245 is made of a silicon nitridebased material, such as SiN and SiON, and the interlayer dielectriclayer 260 is made of a silicon oxide based material, such as SiO₂ or alow-k material. In some embodiments, an annealing operation is performedafter the interlayer dielectric layer is formed.

FIG. 12A shows a perspective view, FIG. 12B is a cross sectional viewalong the Y direction and FIG. 12C is a cross sectional view along the Xdirection, showing one of various stages of the manufacturing operationaccording to an embodiment of the present disclosure. Then, the dummygate electrodes 230 and the dummy gate dielectric layer 215 are removedby using dry and/or wet etching, thereby forming gate spaces 265, asshown in FIGS. 12A-12C. Further, in the gate spaces 265, an interfaciallayer 271 and a dielectric layer 270 are formed as shown in FIGS.12A-12C. As set forth above, the interfacial layer 271 is made ofsilicon oxide, and the dielectric layer 270 is a doped HfO₂ layer.

FIG. 13A shows a perspective view, FIG. 13B is a cross sectional viewalong the Y direction and FIG. 13C is a cross sectional view along the Xdirection, showing one of various stages of the manufacturing operationaccording to an embodiment of the present disclosure. Then, similar tothe operations described with FIGS. 2A-2D, a capping layer (not shown)may optionally be formed, and an annealing operation is performed toconvert the amorphous HfO₂ layer to an orthorhombic HfO₂ layer. Further,a gate electrode 280 is formed, as shown in FIGS. 13A-13C. The cappinglayer and the gate electrode may be formed using a suitable process suchas ALD, CVD, PVD, plating, or combinations thereof. After the conductivematerials for the gate electrode are formed, a planarization operation,such as CMP, is performed to remove excess materials above theinterlayer dielectric layer 260.

After forming the gate structures, further CMOS processes are performedto form various features such as additional interlayer dielectriclayers, contacts/vias, interconnect metal layers, and passivationlayers, etc.

FIGS. 14A-14D show other manufacturing operations for an NC FinFET inaccordance with some embodiments of the present disclosure. Throughoutthe various views and illustrative embodiments, like reference numbersare used to designate like elements. It is understood that additionaloperations can be provided before, during, and after processes shown byFIGS. 14A-15D, and some of the operations described below can bereplaced or eliminated, for additional embodiments of the method. Theorder of the operations/processes may be interchangeable. Material,configuration, dimensions and/or processes the same as or similar to theforegoing embodiments described with respect to FIGS. 1A, 2A-2D and7A-13C may be employed in the following embodiments, and detailedexplanation thereof may be omitted.

As shown in FIG. 14A, the fin structures 320 are patterned by using thehard mask pattern 312, and the isolation insulating layer 325 is formed.Then, a dummy gate dielectric layer (not shown) and a polysilicon layer332 are formed over the fin structures 320, and further a hard maskpattern 334 is formed on the polysilicon layer 332, as shown in FIG.14B. The hard mask pattern 324 includes one or more layers of insulatingmaterial, such as silicon oxide and silicon nitride.

By using the hard mask pattern 334 as an etching mask, the polysiliconlayer 332 is patterned into a dummy gate electrode 332. Further,sidewall spacers 336 are formed on opposing side faces of the dummy gateelectrode 332, and an interlayer dielectric layer 342 is formed, asshown in FIG. 14C. The sidewall spacers 336 include one or more layersof insulating material, such as silicon oxide, silicon nitride andsilicon oxynitride, and the interlayer dielectric layer 342 includes oneor more layers of insulating material such as silicon oxide basedmaterial such as silicon dioxide (SiO₂) and SiON. The material of thesidewall spacers 333 and the material of the interlayer dielectric layer342 are different from each other, so that each of these layers can beselectively etched. In one embodiment, the sidewall spacer 333 is madeof SiOCN, SiCN or SiON and the interlayer dielectric layer 342 is madeof SiO₂.

Then, the dummy gate electrode 332 and the dummy gate dielectric layerare removed by using dry and/or wet etching, thereby forming a gatespace 333, as shown in FIG. 14D.

In the gate space, a first gate dielectric layer 303 and a first gateelectrode 304 are formed as shown in FIGS. 15A and 15B. After theconductive material is formed over the first gate dielectric layer 303,a planarization operation, such as CMP, is performed to form the firstgate electrode 304. The first gate dielectric layer 303 is made of, forexample, a high-k dielectric material, and the first gate electrode 304is made of, for example, a conductive material such as TiN or othermetal material. Further, an etch-back operation is performed to reducethe height of the first gate dielectric layer 303 and the first gateelectrode 304. The conductive material may be formed using a suitableprocess such as ALD, CVD, PVD, plating, or combinations thereof.

Then, a ferroelectric dielectric layer 305 and a second gate electrode306 are formed in the gate space 333, as shown in FIGS. 15C and 15D. Aferroelectric dielectric layer 305 is formed by the operations describedwith respect to FIGS. 2A-2D. A conductive material is formed over theferroelectric dielectric layer 303. After the conductive material isformed over the ferroelectric dielectric layer 305, a planarizationoperation, such as CMP, is performed to form the second gate electrode306, as show in FIGS. 15C and 15D.

After forming the gate structures, further CMOS processes are performedto form various features such as additional interlayer dielectriclayers, contacts/vias, interconnect metal layers, and passivationlayers, etc.

Other methods and structures for manufacturing MIMIS NC FETs aredescribed in U.S. patent application Ser. Nos. 15/476,221 and15/447,479, the entire contents of each of which are incorporated hereinby reference.

It will be understood that not all advantages have been necessarilydiscussed herein, no particular advantage is required for allembodiments or examples, and other embodiments or examples may offerdifferent advantages.

For example, in the present disclosure, a doped HfO₂ having anorthorhombic crystal phase is employed for an NC FET. By using a cappingmetallic layer during an annealing operation, it is possible toeffectively convert an amorphous structure of the as-deposited HfO₂layer to an orthorhombic crystal structure. As compared to otherperovskite ferroelectric films (such as, PZT or BaTiO₃), theferroelectric HfO₂ disclosed herein can maintain polarization withoutdegradation down to 3 nm.

In accordance with an aspect of the present disclosure, in a method ofmanufacturing a negative capacitance structure, a dielectric layer isformed over a substrate. A first metallic layer is formed over thedielectric layer. After the first metallic layer is formed, an annealingoperation is performed, followed by a cooling operation. A secondmetallic layer is formed. After the cooling operation, the dielectriclayer becomes a ferroelectric dielectric layer including an orthorhombiccrystal phase. In one or more of the foregoing or following embodiments,the dielectric layer includes HfO₂ doped with one or more selected fromthe group consisting of Si, Zr, Al, La, Y, Gd and Sr. In one or more ofthe foregoing or following embodiments, the dielectric layer includesHfO₂ doped with Si in an amount of 2-6 mol % or HfZrO₂. In one or moreof the foregoing or following embodiments, the annealing operation isperformed at a temperature in a range from 700° C. to 1000° C. in aninert gas ambient. In one or more of the foregoing or followingembodiments, the second metallic layer is formed after the coolingoperation. In one or more of the foregoing or following embodiments, thefirst metallic layer includes TiN or TiN doped with Si. In one or moreof the foregoing or following embodiments, the second metallic layer isTaN. In one or more of the foregoing or following embodiments, theorthorhombic crystal phase is polycrystalline. In one or more of theforegoing or following embodiments, the dielectric layer as formed isamorphous.

In accordance with another aspect of the present disclosure, in a methodof manufacturing a negative capacitance field effect transistor(NC-FET), a dielectric layer is formed over a channel layer. A cappingmetallic layer is formed over the dielectric layer. After the cappingmetallic layer is formed, an annealing operation is performed, followedby a cooling operation. A barrier layer is formed over the cappinglayer. A work function adjustment layer is formed over the barrierlayer. After the cooling operation, the dielectric layer becomes aferroelectric dielectric layer including an orthorhombic crystal phase.In one or more of the foregoing or following embodiments, the dielectriclayer includes HfO₂ containing Si or HfO₂ containing Zr. In one or moreof the foregoing or following embodiments, the annealing operation isperformed at a temperature in a range from 700° C. to 1000° C. in aninert gas ambient. In one or more of the foregoing or followingembodiments, the capping metallic layer includes TiN or TiN doped withSi. In one or more of the foregoing or following embodiments, thebarrier layer is formed after the cooling operation. In one or more ofthe foregoing or following embodiments, the barrier layer is TaN. In oneor more of the foregoing or following embodiments, a gate metal layer isfurther formed over the work function adjustment layer. In one or moreof the foregoing or following embodiments, a glue layer is furtherformed over the work function adjustment layer before the gate metallayer is formed. In one or more of the foregoing or followingembodiments, an interfacial oxide layer is further formed over thechannel layer before the dielectric layer is formed.

In accordance with another aspect of the present disclosure, in a methodof manufacturing a negative capacitance fin field effect transistor(NC-FinFET), a dummy gate structure is formed over a fin structure. Asource/drain structure is formed over the fin structure on opposingsides of the dummy gate structure. An interlayer dielectric layer isformed over the source/drain structure. The dummy gate structure isremoved, thereby exposing a channel region of the fin structure. Adielectric layer is formed over the channel region. A capping metalliclayer is formed over the dielectric layer. After the capping metalliclayer is formed, an annealing operation is performed, followed by acooling operation. A gate electrode including one or more metalliclayers is formed. After the cooling operation, the dielectric layerbecomes a ferroelectric dielectric layer including an orthorhombiccrystal phase. In one or more of the foregoing or following embodiments,the dielectric layer including an orthorhombic crystal phase includesHfO₂ containing Si or HfO₂ containing Zr, and further includes Ti.

In accordance with one aspect of the present disclosure, a negativecapacitance structure includes a first conductive layer, a ferroelectricdielectric layer disposed over the first conductive layer, and a secondconductive layer disposed over the ferroelectric dielectric layer. Theferroelectric dielectric layer includes an orthorhombic crystal phase.In one or more of the foregoing or following embodiments, theferroelectric dielectric layer includes HfO₂ doped with one or moreselected from the group consisting of Si, Zr, Al, La, Y, Gd and Sr. Inone or more of the foregoing or following embodiments, the ferroelectricdielectric layer includes HfO₂ doped with at least one selected from thegroup consisting of Si and Zr. In one or more of the foregoing orfollowing embodiments, the ferroelectric dielectric layer furtherincludes Ti in an amount of 2-5 mol %. In one or more of the foregoingor following embodiments, the ferroelectric dielectric layer furtherincludes Al in an amount of 5-7 mol %. In one or more of the foregoingor following embodiments, the ferroelectric dielectric layer includesHfO₂ doped with Si in an amount of 2-6 mol %. In one or more of theforegoing or following embodiments, the ferroelectric dielectric layerincludes HfZrO₂. In one or more of the foregoing or followingembodiments, the second metallic layer includes TiN or TiN doped withSi.

In accordance with another aspect of the present disclosure, a negativecapacitance field effect transistor (NC-FET) includes a channel layermade of a semiconductor, a ferroelectric dielectric layer disposed overthe channel layer, and a gate electrode layer disposed over theferroelectric dielectric layer. The ferroelectric dielectric layerincludes an orthorhombic crystal phase. In one or more of the foregoingor following embodiments, the ferroelectric dielectric layer includesHfO₂ doped with one or more selected from the group consisting of Si,Zr, Al, La, Y, Gd and Sr. In one or more of the foregoing or followingembodiments, the ferroelectric dielectric layer includes HfO₂ doped withat least one selected from the group consisting of Si and Zr. In one ormore of the foregoing or following embodiments, the gate electrode layerincludes a first conductive layer disposed on the ferroelectricdielectric layer, and the first conductive layer is made of TiN or TiNdoped with one or more elements. In one or more of the foregoing orfollowing embodiments, the gate electrode layer further includes asecond conductive layer disposed on the first conductive layer, and thesecond conductive layer is made of TaN. In one or more of the foregoingor following embodiments, the gate electrode layer further includes awork function adjustment layer disposed on the second conductive layer,and a tungsten layer disposed over the work function adjustment layer.In one or more of the foregoing or following embodiments, the NC-FET isa p-type FET and the work function adjustment layer includes TiN. In oneor more of the foregoing or following embodiments, the ferroelectricdielectric layer further includes Ti in an amount of 2-5 mol %. In oneor more of the foregoing or following embodiments, the NC-FET is ann-type FET and the work function adjustment layer includes TiAl. In oneor more of the foregoing or following embodiments, the ferroelectricdielectric layer further includes Al in an amount of 5-7 mol %. In oneor more of the foregoing or following embodiments, the NC-FET is a finFET and the channel layer is a part of a fin structure.

In accordance with another aspect of the present disclosure, a negativecapacitance field effect transistor (NC-FET) includes a channel layermade of a semiconductor, a first dielectric layer disposed over thechannel layer, a first conductive layer disposed over the firstdielectric layer, a second dielectric layer disposed over the firstconductive layer, and a gate electrode layer disposed over the seconddielectric layer. The second dielectric layer includes HfO₂ having anorthorhombic crystal phase.

The foregoing outlines features of several embodiments or examples sothat those skilled in the art may better understand the aspects of thepresent disclosure. Those skilled in the art should appreciate that theymay readily use the present disclosure as a basis for designing ormodifying other processes and structures for carrying out the samepurposes and/or achieving the same advantages of the embodiments orexamples introduced herein. Those skilled in the art should also realizethat such equivalent constructions do not depart from the spirit andscope of the present disclosure, and that they may make various changes,substitutions, and alterations herein without departing from the spiritand scope of the present disclosure.

What is claimed is:
 1. A negative capacitance structure, comprising: afirst conductive layer; a ferroelectric dielectric layer disposed overthe first conductive layer; and a second conductive layer disposed overthe ferroelectric dielectric layer, wherein the ferroelectric dielectriclayer includes an orthorhombic crystal phase.
 2. The negativecapacitance structure of claim 1, wherein the ferroelectric dielectriclayer includes HfO₂ doped with one or more selected from the groupconsisting of Si, Zr, Al, La, Y, Gd and Sr.
 3. The negative capacitancestructure of claim 1, wherein the ferroelectric dielectric layerincludes HfO₂ doped with at least one selected from the group consistingof Si and Zr.
 4. The negative capacitance structure of claim 3, whereinthe ferroelectric dielectric layer further includes Ti in an amount of2-5 mol %.
 5. The negative capacitance structure of claim 3, wherein theferroelectric dielectric layer further includes Al in an amount of 5-7mol %.
 6. The negative capacitance structure of claim 1, wherein theferroelectric dielectric layer includes HfO₂ doped with Si in an amountof 2-6 mol %.
 7. The negative capacitance structure of claim 1, whereinthe ferroelectric dielectric layer includes HfZrO₂.
 8. The negativecapacitance structure of claim 1, wherein the second metallic layerincludes TiN or TiN doped with Si.
 9. A negative capacitance fieldeffect transistor (NC-FET), comprising: a channel layer made of asemiconductor; a ferroelectric dielectric layer disposed over thechannel layer; and a gate electrode layer disposed over theferroelectric dielectric layer, wherein the ferroelectric dielectriclayer includes an orthorhombic crystal phase.
 10. The NC-FET of claim 9,wherein the ferroelectric dielectric layer includes HfO₂ doped with oneor more selected from the group consisting of Si, Zr, Al, La, Y, Gd andSr.
 11. The NC-FET of claim 9, wherein the ferroelectric dielectriclayer includes HfO₂ doped with at least one selected from the groupconsisting of Si and Zr.
 12. The NC-FET of claim 11, wherein: the gateelectrode layer includes a first conductive layer disposed on theferroelectric dielectric layer, and the first conductive layer is madeof TiN or TiN doped with one or more elements.
 13. The NC-FET of claim12, wherein: the gate electrode layer further includes a secondconductive layer disposed on the first conductive layer, and the secondconductive layer is made of TaN.
 14. The NC-FET of claim 13, wherein:the gate electrode layer further includes a work function adjustmentlayer disposed on the second conductive layer, and a tungsten layerdisposed over the work function adjustment layer.
 15. The NC-FET ofclaim 14, wherein the NC-FET is a p-type FET and the work functionadjustment layer includes TiN.
 16. The NC-FET of claim 15, wherein theferroelectric dielectric layer further includes Ti in an amount of 2-5mol %.
 17. The NC-FET of claim 14, wherein the NC-FET is an n-type FETand the work function adjustment layer includes TiAl.
 18. The NC-FET ofclaim 17, wherein the ferroelectric dielectric layer further includes Alin an amount of 5-7 mol %.
 19. The NC-FET of claim 9, wherein the NC-FETis a fin FET and the channel layer is a part of a fin structure.
 20. Anegative capacitance field effect transistor (NC-FET), comprising: achannel layer made of a semiconductor; a first dielectric layer disposedover the channel layer; a first conductive layer disposed over the firstdielectric layer; a second dielectric layer disposed over the firstconductive layer; and a gate electrode layer disposed over the seconddielectric layer, wherein the second dielectric layer includes HfO₂having an orthorhombic crystal phase.